TW201611084A - Ultraclean autosampler with syringe delivery for mass spectrometry - Google Patents

Abstract

A system can include a valve assembly including a first valve and a second valve in fluid communication with the first valve. The valve assembly can be configured to deliver one or more of a sample, a chemical (e.g., an acid, a base, an organic chemical, etc.), and a standard via flow of a working fluid facilitated by one or more syringe pumps. Further, the one or more of the sample, the chemical, and the standard can maintain a physical separation from the one or more syringe pumps during delivery of the one or more of the sample, the chemical, and the standard.

Description

Ultra-purified autosampler with syringe delivery for mass spectrometry [Cross-Reference to Related Applications]

The present application claims the benefit of U.S. Provisional Application Serial No. 62/039,315, filed on Aug. 19, 2014, which is incorporated herein by reference. The entire disclosure of U.S. Provisional Application Serial No. 62/039,315 is incorporated herein by reference.

Inductively Coupled Plasma (ICP) Spectroscopy is an analytical technique commonly used to determine trace element concentrations and isotope ratios in liquid samples. ICP spectroscopy uses partially ionized argon plasma generated electromagnetically, which reaches a temperature approaching 7000K. When the same is introduced into the plasma, the high temperature causes the sample atoms to become ionized or emit light. Since each chemical element produces a characteristic mass or emission spectrum, measuring the emitted mass or spectrum of light allows for determining the elemental composition of the original sample.

A sample introduction system can be employed to introduce a liquid sample into an ICP spectrometer (eg, an inductively coupled plasma mass spectrometer (ICP/ICP-MS), an inductively coupled plasma atomic emission spectrometer (ICP-AES), or It is used in the analysis). For example, the present introduction system can dispense a liquid sample from a container and then transport the liquid to a sprayer, which converts the liquid to an ICP spectrometer suitable for use in plasma. A polydisperse aerosol that is ionized. The aerosol is then stored in a spray chamber to remove larger aerosol particles. Once leaving the spray chamber, the aerosol is either ICP-MS or ICP-AES One of the instrument's plasma torch assemblies is introduced into the plasma for analysis.

A system can include a valve assembly including a first valve and a second valve in fluid communication with the first valve. The valve assembly can be configured to deliver the same, a chemical (eg, an acid, a base, an organic chemical, etc.) and a standard via the flow of one of the working fluids assisted by one or more syringe pumps One or more of the products. Further, the one or more of the sample, the chemical, and the standard may be maintained with the one or more during delivery of the sample, the chemical, and the one or more of the standard One of the syringe pumps is physically separated.

This [invention] is provided to introduce one of the concepts in a simplified form, which is further described in the following [Embodiment]. This Summary is not intended to identify key features or essential features of the claimed subject matter, and is not intended to be used as an aid in determining the scope of the claimed subject matter.

100‧‧‧ system

102‧‧‧ circuit

104‧‧‧ pump

106‧‧‧Ion exchange section

108‧‧‧Three-way connector

110‧‧‧Management

112‧‧‧Syringe pump

112a‧‧Injector pump

112b‧‧"Syringe pump

112c‧‧"Syringe pump

112d‧‧‧Syringe pump

114‧‧‧ valve

116‧‧‧ Carrier

118‧‧‧Internal standard

120‧‧‧Ion exchange section

122‧‧‧ valve

124‧‧‧Autosampler

126‧‧‧sample loop

128‧‧‧ sprayer

130‧‧‧ cyclone spray chamber

132‧‧‧Inductively Coupled Plasma (ICP) Torch

200‧‧‧Transportation section

202‧‧‧Valve

204‧‧‧ purified fluid

206a‧‧‧ fluid line

206b‧‧‧ fluid line

206c‧‧‧ fluid line

206d‧‧‧ fluid line

208a‧‧‧ fluid line

208b‧‧‧ fluid line

208c‧‧‧ fluid line

208d‧‧‧ fluid line

Paragraph 210a‧‧

210b‧‧‧

210c‧‧‧

300‧‧‧ valve assembly

302‧‧‧sample loop

304‧‧‧ standard circuit

306‧‧‧Chemical circuit

308a‧‧‧ fluid line

308b‧‧‧ fluid line

308c‧‧‧ fluid line

310a‧‧‧Loader

310b‧‧‧Loader

310c‧‧‧Loader

312‧‧‧ mixed 埠

314‧‧‧Inductively Coupled Plasma Mass Spectrometer (ICP-MS)

316‧‧‧ valve

Reference is made to the accompanying drawings to describe the embodiments.

1 is an illustration of a system in accordance with an example embodiment of the present invention configured to deliver a purified fluid (eg, to a mass spectrometry system).

2 is an illustration of a system in accordance with an example embodiment of the present invention configured to introduce a purified fluid into a portion of the system and introduce a purified fluid as a working fluid within the system.

3 is a graphical illustration of a system for providing ultra-purified dilution and chemical (eg, acidic) spikes for in-line preparation for determining high purity chemicals by ICP-MS, in accordance with an example embodiment of the present invention. A trace amount of metal.

A sample introduction system can be employed to introduce a liquid sample into an ICP spectrometer for analysis. For example, a plurality of in-line injectors can be used to automatically deliver the same (which has been loaded into a first valve circuit) to a nebulizer at a controlled rate using a plurality of in-line injectors. Perform other dilutions and/or standard spikes as appropriate. Examples include successive spikes of samples such as automatic in-line dilution prior to analysis, automatic addition of internal standard solutions, and methods of standard solutions or other solutions to addition or other applications. The presence of contaminants in the syringe fluid pumped by one or more syringe pumps can cause measurement errors due to the analysis of the metal at a relatively low level (e.g., less than five tenths (5 ppt)). Further, certain solutions used as standards or spikes may be detrimental to portions of the system if allowed to contact certain areas with the sample introduction system. For example, a purge section (eg, a section that uses an ion exchange resin to remove impurities from a working fluid (such as high purity water)) can release trapped impurities upon exposure to an acidic solution. If an acidic solution is used as a standard or a spike solution, the acidic solution can cause the captured impurities to be released into the system, resulting in erroneous introduction. In addition, the introduction of any contaminated fluid can provide erroneous test conditions when analyzing trace amounts of materials (eg, trace metals) in high purity chemicals. For example, a syringe pump for controlled fluid delivery can introduce contaminants when different fluids are allowed to contact the syringe pump.

Accordingly, systems and methods for delivering purified fluids, such as ultra high purity water, are described, wherein the systems maintain a sample solution, a standard solution, and a chemical (eg, acidic, basic, organic, etc.) solution and A physical separation of the syringe pump that drives the working fluid through the system to drive the sample solution, standard solution, and chemical solution. The systems and methods described herein can include in-line preparation of syringes for the determination of trace amounts of materials (eg, trace metals) in high purity chemicals by ICP-MS to provide ultra-purification dilution and chemical spikes. System and method.

Referring generally to Figure 1, an example system 100 configured to deliver a purified fluid is depicted. A system 100 includes a purifier configured to purify a fluid (eg, to produce deionized (DI) water) (eg, a pump 104 and an ion exchange section 106 (such as a cation exchange section)). Pump 104 and ion exchange section 106 can be positioned at a first location. System 100 also includes a configuration configured to cycle the purified fluid between the purifier and the second location at the first location The primary circuit 102 can be remote from the first location (eg, several meters away from the first location, several meters away from the first location, etc.) or can be located at the same location. System 100 further includes a connector (eg, a manifold 110) at the second location. In some embodiments, loop 102 is coupled to manifold 110 via a three-way connector 108. Manifold 110 is configured to be coupled to, for example, a mass spectrometry apparatus to supply DI water to the mass spectrometry apparatus.

In some embodiments, manifold 110 is coupled to one or more syringe pumps 112, and one or more syringe pumps 112 can be configured to utilize the DI water (and possibly diluents and/or carriers 116, internal standards 118 Etc.) supplied to the mass spectrometry equipment. For example, a valve 114 (eg, a rotary valve) is coupled to the syringe pump 112. In some embodiments, one or more purification sections (eg, additional ion exchange sections 120 (such as additional cation exchange sections), etc.) are disposed between valve 114 and another valve 122 (eg, a second rotary valve), Valve 122 can be coupled to a sampler assembly (such as an autosampler 124) for automatically collecting the same samples from a plurality of samples contained in a test tube. In some embodiments, a system 100 can be used to deliver DI water having a concentration of one of less than one trillionth (ppt) of one of the contaminant elements, such as sodium (Na).

System 100 can also include a switching valve having a plurality of positions that can select a source of the injector fluid. The syringe fluid can have a pH or ionic strength that allows contaminants in the syringe fluid to be confined in the purge section. The switching valve can also be selected to have a second syringe fluid capable of regenerating one of the pH or ionic strength of the purge section.

The system 100 can also include a sprayer 128 coupled to a cyclonic spray chamber 130 for supplying sample gas to an inductively coupled plasma (ICP) torch 132 from the autosampler 124, internal standard 118, carrier 116, DI water. Wait. Valve 122 can be coupled to autosampler 124, nebulizer 128, and valve 114. Valve 122 may receive a sample from autosampler 124, internal standard 118, carrier 116, and/or DI water and supply it to nebulizer 128. Valve 122 may also be coupled to the same circuit 126 for holding a fill fluid or the like. A peristaltic pump can also be used to evacuate the waste from the atomizer 128. For example, the peristaltic pump can be connected to a nebulizer One of the discharge chambers of 128.

Referring to FIG. 2, a delivery portion 200 that introduces a purified fluid into a portion of system 100 and introduces the purified fluid as one of the working fluids within system 100 is shown. The purified fluid can comprise, for example, ultra high purity water (such as deionized water having a concentration of one of less than one trillion (ppt) of one of the contaminant elements (such as sodium (Na)). Delivery portion 200 includes a valve 202 (e.g., a rotary valve) in fluid communication with a plurality of syringe pumps 112 (showing four syringe pumps, such as labels 112a, 112b, 112c, 112d). Valve 202 is also in fluid communication with a source of purified fluid 204. In an embodiment, the source of purified fluid 204 is a fluid purified by ion exchange section 106 as shown in FIG. In an embodiment, the source of purified fluid 204 is a container of one of the purified fluids. In an embodiment, having a pH or ionic strength capable of regenerating one or more purification stages of system 100 can be introduced to delivery portion 200 as purified fluid 204 distributed throughout one or more portions of the system.

Valve 202 is switchable between two operating positions. In a first operational position of valve 202, syringe pump 112 draws the purified fluid from the source of purified fluid 204 into valve 202 and the coupled fluid line. For example, syringe pump 112a can draw purified fluid into fluid line 206a, syringe pump 112b can draw purified fluid into fluid line 206b, syringe pump 112c can draw purified fluid into fluid line 206c, and syringe pump 112d may draw the purified fluid into fluid line 206d. In a second operational position of valve 202, the syringe pumps drive the purified fluid from the fluid lines (eg, fluid lines 206a, 206b, 206c, 206d) to other portions of system 100, further herein. description. For example, syringe pump 112a can drive the fluid from fluid line 206a to fluid line 208a, syringe pump 112b can drive the fluid from fluid line 206b to fluid line 208b, and syringe pump 112c can drive the fluid from fluid line 206c to fluid line 208c, And the syringe pump 112d can drive the fluid from the fluid line 206d to the fluid line 208d. In an embodiment, the valve 202 is in fluid communication with one or more purge sections configured to treat the purified fluid prior to entering the other portion of the system 100. The one or more purification sections are allowing the purification The purity of the purified fluid is ensured prior to fluid manipulation throughout the portion of the system. For example, fluid line 208a can be coupled between valve 202 and a purge section 210a, fluid line 208b can be coupled between valve 202 and a purge section 210b, and fluid line 208c can be coupled between valve 202 and a purge section 210c. And fluid line 208d can be coupled between valve 202 and a purge section 210d. The flow from each of the segments (210a, 210b, 210c, 210d) to the system 100 will be described with further reference to FIG.

Referring to Figure 3, there is shown in-line for providing ultra-purification dilution and chemical (e.g., acidic, basic, organic, etc.) spikes (e.g., for determining trace metals in high purity chemicals by ICP-MS) A valve assembly 300 is prepared. Valve assembly 300 includes a first valve (shown as valve 114) in fluid communication with a second valve (shown as valve 122). In an embodiment, the valve 114 is configured to be driven via fluid line 208a (eg, driven by syringe pump 112a), fluid line 208b (eg, driven by syringe pump 112b), and fluid line 208d (eg, by syringe pump 112d) The coupled fluid receives the purified fluid, and the valve 122 is configured to receive the purified fluid via coupling with a fluid line 208c (eg, driven by a syringe pump 112c). Valve assembly 300 includes one or more holding circuits in fluid communication with valve 114 and valve 122. For example, FIG. 3 shows one sample circuit 302 in fluid communication with valve 114 and valve 122 (eg, coupled between valve 114 and valve 122) in fluid communication with valve 114 and valve 122 (eg, at valve 114 and valve 122) One of the standard circuits 304 and one of the chemical circuits 306 in fluid communication with the valves 114 and 122 (e.g., coupled between the valve 114 and the valve 122). Chemical circuit 306 may refer to a circuit configured to hold a chemical, such as a spike solution, within system 100, and may include, but is not limited to, an acidic, a basic, an organic chemistry Products and similar. In an embodiment, sample loop 302 may correspond to sample loop 126 described with reference to FIG. In one embodiment, the sample loop 302 has a volume of approximately 2.5 milliliters (2.5 mL) and the standard loop 304 has a volume between approximately 0.3 milliliters (0.3 mL) and 3.0 milliliters (3.0 mL), and the chemical loop 306 has a volume between approximately 0.3 mL (0.3 mL) and 3.0 mL (3.0 mL). As used herein, the term "loop" (eg, sample loop) 302, standard circuit 304, chemical circuit 306) may refer to a wound fluid line, a DC body line, a curved fluid line, a container, or other structure having a defined volume to hold and transfer fluid.

In an embodiment, the valve 122 is configured to receive the same (eg, via fluid line 308a), a standard (eg, via fluid line 308b), and a chemical (eg, an acidic, alkaline, An organic chemical, etc.) (eg, via fluid line 308c). In an embodiment, the standard can correspond to internal standard 118. For example, the sample can be obtained via autosampler 124 and drawn into valve assembly 300 and to sample loop 302 via a loader 310a (eg, a pressure source or a negative pressure source (such as a syringe pump or vacuum cleaner)). The standard may be drawn into the valve assembly 300 and into the standard circuit 304 via a loader 310b (eg, a pressure source or a negative pressure source (such as a syringe pump or vacuum cleaner), and the chemical It can be drawn into the valve assembly 300 and into the chemical circuit 306 via a loader 310c (eg, a pressure source or a negative pressure source such as a syringe pump or vacuum cleaner).

In an embodiment, each of valve 114 and valve 122 is switchable between a first operational position and a second operational position. For example, in the first operational position, the sample can be drawn into the valve assembly 300 and into the sample circuit 302, the standard can be drawn into the valve assembly 300 and into the standard circuit 304, and the chemical It can be drawn into the valve assembly 300 and into the chemical circuit 306. In the second operational position, the sample is driven from sample loop 302 via flow of the purified fluid (e.g., working fluid) supplied through fluid line 208b by syringe pump 112b via a syringe pump 112d While the flow of the purified fluid (e.g., working fluid) supplied through fluid line 208d is driven from standard loop 304, the chemical is supplied to the purified fluid through fluid line 208a via syringe pump 112a ( For example, the flow of working fluid is driven from chemical loop 306. Accordingly, the sample remains physically separated from the syringe pump 112b, the standard remains physically separated from the syringe pump 112d, and the chemical remains physically separated from the syringe pump 112a, whereby only the purified A fluid (eg, a working fluid) interacts with the sample, the standard, and the chemical to drive the sample, the standard, and the chemical from their respective held loops.

In an embodiment, the sample, the standard, and the chemical are driven from sample loop 302, standard loop 304, and chemical loop 306 to one of valves 122, 埠 312. The mixing bowl 312 can also be in fluid communication with the fluid line 208c to receive one of the purified fluid (eg, diluent) supplied by the syringe pump 112c for flow with the sample, the standard, and the chemical at the mixing bowl 312 Or more than mixing and/or diluting the sample, standard, and one or more of the chemicals. In an embodiment, the sample, the standard, the chemical, and the diluent are received substantially simultaneously by the mixing bowl 312. In an embodiment, system 100 includes a timer configured to drive syringe pump 112c for a specified time to provide a flow of the diluent to mixing bowl 312, wherein the specified time can include the sample, the standard, and One or more of the chemicals are substantially simultaneously one time, different from the sample, the standard, and one or more of the chemical, and the like. In an embodiment, the valve 114 is coupled to a source of the diluent and is configured to load the diluent into a diluent loop coupled between the valve 114 and the valve 122 for diluting the diluent from the diluent The agent circuit is introduced into the mixing bowl 312.

Valve 122 is in fluid communication with an inductively coupled plasma mass spectrometer (ICP-MS) 314. For example, the mixing bowl 312 can be coupled to a valve 316 (eg, a transfer valve) configured to transfer the mixed sample solution from the mixing bowl 312 to the ICP-MS 314 for analysis. In an embodiment, system 100 can be purged, drained, refilled, or the like between sample cycles. For example, the sample loop can be purged between sample runs (eg, via a working fluid, an acidic solution, an alkaline solution, an organic solution, a solvent, etc.) and/or refilled. Standard loop 304 and chemical loop 306 can also be refilled between sample cycles. For example, at least a portion of the standard loop 304 or the entire standard loop 304 can be refilled between sample runs, at least a portion of the chemical loop 306 or the entire chemical loop 306 can be refilled between sample loops, and Similar. Refill these circuits to prevent dirty solutions Within the system 100, diffusion effects can be prevented from affecting one or more of the valves of the system 100, and the like.

Although the subject matter of the language is described in terms of structural features and/or processing operations, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the particular features or acts described. The specific features and behaviors described above are disclosed as examples of the scope of the patent application.

100‧‧‧ system

102‧‧‧ circuit

104‧‧‧ pump

106‧‧‧Ion exchange section

108‧‧‧Three-way connector

110‧‧‧Management

112‧‧‧Syringe pump

114‧‧‧ valve

116‧‧‧ Carrier

118‧‧‧Internal standard

120‧‧‧Ion exchange section

122‧‧‧ valve

124‧‧‧Autosampler

126‧‧‧sample loop

128‧‧‧ sprayer

130‧‧‧ cyclone spray chamber

132‧‧‧Inductively Coupled Plasma (ICP) Torch

Claims (20)

A system comprising: a first valve; a second valve in fluid communication with the first valve, the second valve comprising a mixing cartridge; and a present circuit coupled to the first valve and the second valve a standard circuit coupled between the first valve and the second valve; a chemical circuit coupled between the first valve and the second valve; one or more syringe pumps, The device is configured to drive a working fluid through at least a portion of the first valve; wherein each of the first valve and the second valve is switchable between a first position and a second position, wherein In the first position, the same load is loaded into the sample loop via the same loader, a standard is loaded into the standard circuit via a standard loader, and a chemical is passed through a chemical loader. Loading into the chemical circuit, and wherein in the second position, the sample is delivered from the sample circuit to the mixing bowl of the second valve via the flow of the working fluid, the standard flows through the working fluid And from the standard circuit to the second valve Mixing the crucible and the chemical is transferred from the chemical loop to the mixing bowl of the second valve via the flow of the working valve, the sample, the standard and the chemical in the sample, the standard, and the chemical Maintaining physical separation from the one or more syringe pumps during delivery to the mixing bowl. The system of claim 1, wherein the standard loop and one or more of the chemical loops are refilled between sample runs. The system of claim 1 wherein the mixed helium is in fluid communication with an inductively coupled plasma mass spectrometer (ICP-MS). The system of claim 1, wherein the second valve comprises one configured to receive a high purity diluent, the crucible being in fluid communication with the mixing crucible. The system of claim 4, wherein the mix is configured to receive the sample, the standard, the chemical, and the high purity diluent substantially simultaneously. The system of claim 1, further comprising: a purifier in fluid communication with the first valve, the purifier being configured to purge fluid to provide the working fluid to the first valve. A system comprising: a valve assembly including a first valve and a second valve in fluid communication with the first valve, the valve assembly configured to be assisted by one or more syringe pumps The flow of the working fluid delivers one or more of the same, a chemical, and a standard, and the one or more of the sample, the chemical, and the standard are in the sample, the chemical, and the standard The one or more are maintained separated from one of the one or more syringe pumps during delivery. The system of claim 7, wherein each of the first valve and the second valve is switchable between a first position and a second position, wherein the sample, the chemical, and The one or more of the standards are captured by a movement of one or more loaders into a holding loop in fluid communication with each of the first valve and the second valve. The system of claim 8, wherein the one or more loaders comprise at least one of a syringe pump and a vacuum loader. The system of claim 8, wherein in the second position, the one or more of the sample, the chemical, and the standard are delivered to the mixing valve of the second valve via the flow of the working fluid. The system of claim 10, wherein the mixed helium is in fluid communication with an inductively coupled plasma mass spectrometer (ICP-MS). The system of claim 7, further comprising at least one of: the same circuit coupled between the first valve and the second valve; a standard circuit coupled to the first valve and the first Between the two valves; and a chemical circuit coupled between the first valve and the second valve. The system of claim 12, wherein the first valve and the second valve are switchable between a first position and a second position, wherein in the first position, the same load is loaded via the same loader In the sample loop, a standard is loaded into the standard loop via a standard loader and a chemical is loaded into the chemical loop via a chemical loader. The system of claim 13, wherein in the second position, the sample is delivered from the sample loop to one of the second valves via a flow of the working fluid assisted by a first syringe pump, the standard Delivering from the standard circuit to the mixing bowl of the second valve via the flow of the working fluid assisted by a second syringe pump, and the chemical flows through the working fluid assisted by a third syringe pump The mixing raft is delivered from the chemical circuit to the second valve. The system of claim 14, further comprising one or more of: a first purification section coupled between the first syringe pump and the first valve; a second purification section coupled to the first a second syringe pump and the first valve; and a third purification section coupled between the third syringe pump and the first valve. The system of claim 15 wherein one or more of the first purification section, the second purification section, and the third purification section comprise an ion exchange resin. The system of claim 14, wherein the second valve comprises a stack configured to receive one of the diluents assisted by a diluent syringe pump. The system of claim 17, wherein the diluent comprises high purity deionized water. The system of claim 17, further comprising: A purge section coupled between the diluent syringe pump and the second valve. The system of claim 7, further comprising: a purifier in fluid communication with the valve assembly, the purifier being configured to purge fluid to provide the working fluid to the valve assembly.